CH 23 CARBOHYDRATES

- carbohydrates are the most abundant molecules found in nature

- these complex multifunctional compounds exhibit classic organic chemical behavior in the
execution of myriad important biological applications

CLASSIFICATION –
Original Definition % hydrate of carbon, Cn(H2O)m (a common molecular formula)

Modern Definition % a polyhydroxyaldehyde, a polyhydroxyketone or a compound which easily

hydrolyzes to either of them

Saccharide, S % a sugar unit (from Latin for sweet)

Carbohydrate Hierarchy –

H H H
Polysaccharide Oligosaccharide Disaccharide Monosaccharide
H2O, ∆ H2O, ∆ H2O, ∆
(polymer) (oligomer) (dimer) (monomer)

S Sn S S Sn S S S S

103 's units 10 - 102 's units 2 units 1 unit

Monosaccharides & Disaccharides are commonly referred to as “simple sugars”

I. MONOSACCHARIDES –
- the structural characteristics of monosaccharides are fundamental to all carbohydrates

CLASSIFICATION –

- specific monosaccharides are usually referred to by their common names, but general
classifications exist which are based on common structural features

A. Functional Group –

- every carbon in a monosaccharide is oxygenated (with a carbonyl =O or a hydroxyl -OH)

- monosaccharides can be classified according to the type of carbonyl group present:

 Functional Group General Structural Formula Name Prefix Suffix
H CHO
C O (CHOH)n Aldose aldo- -ose
R
CH2OH
(Aldehyde)
CH2OH
R
C O C O Ketose keto- -ose
R (CHOH)n
(Ketone) CH2OH

B. Number of Carbons –

- monosaccharides can be classified according to the number of carbons present:

# C's = 3 4 5 6 7 ...........

Name = triose tetrose pentose hexose heptose ............

(Suffix)

EX. classify according to FG & #C’s

CH2OH
CHO C O
CHOH CHOH
CHOH CHOH
CH2OH CH2OH
an aldotetrose a 2-ketopentose

C. D & L Configuration –

- all CHOH group carbons in monosaccharides are stereocenters (C*)

- the D/L configuration of all carbohydrates is based on the stereocenter contained in the simple
aldotriose, glyceraldehyde

CHO CHO
H OH HO H
CH2OH CH2OH

D-(+)-glyceraldehyde L-(-)-glyceraldehyde
(R-configuration) (S-configuration)

- all D-series sugars can be degraded to D-(+)-glyceraldehyde

- all L-series sugars can be degraded to L-(-)-glyceraldehyde

Assigning the D/L Series Configuration –

- place the most oxidized carbon (C=O) closest to the “top” in a Fischer projection (FP)

- examine the configuration of the CHOH closest to the “bottom” (2nd to “last” C in the FP)

-OH Right % D-Series -OH Left % L-Series

CH2OH CH2OH
CHO CHO C O C O
(CHOH)n (CHOH)n (CHOH)n (CHOH)n
H OH HO H H OH HO H
CH2OH CH2OH CH2OH CH2OH
D-aldoses L-aldoses D-ketoses L-ketoses
EX ‘s CHO CHO CH2OH CH2OH
H OH HO H
C O C O
HO H H OH HO H H OH
H OH HO H H OH HO H
H OH HO H H OH HO H
CH2OH CH2OH CH2OH CH2OH
D-(+)-glucose L-(-)-glucose D-(-)-fructose L-(+)-fructose

- most naturally occurring sugars are D-series

Family of D-Aldoses
EPIMERS –

C*) only
- a pair of sugars which differ in configuration at one asymmetric carbon (C

- while the unique configuration can exist at any stereocenter, the most common class of epimers
differ in configuration at C-2 (in which case the carbon’s number may be understood & omitted)

- epimers are a class of diastereomers (stereoisomers which are not mirror image enantiomers)

- the arrows in the family of D-aldoses (shown on previous page) relate pairs of C-2 epimers

Other EX ‘s 1 1
1 1
CHO CHO
CHO CHO 2
HO 2
H HO H
2 2
H OH H OH 3
HO 3
H HO H
3 3
H OH HO H 4
H 4
OH HO H
4 4
H OH H OH 5
5 H 5
OH H OH
5
CH2OH CH2OH 6 6
CH2OH CH2OH
D-ribose D-xylose
D-mannose D-talose
aldopentoses which are C-3 epimers aldohexoses which are C-4 epimers

CYCLIC STRUCTURES OF MONOSACCHARIDES –

- recall that the intramolecular addition reaction of a ( or *-hydroxycarbonyl compound results in

the formation of a cyclic hemiacetal
O OH
C C
n = 3 or 4
(C)n (C)n
H ring = 5 or 6 member
O O

hydroxy aldehyde cyclic hemiacetal

or
hydroxy ketone

- monosaccharides exist predominately (>99%) in this more stable cyclic hemiacetal form

- aldohexoses form six-membered ring hemiacetals, while aldopentoses & ketohexoses form five-
membered ring hemiacetals
OH HO
O R
O
HO OH OH
HO OH
HO OH
aldopentoses & ketohexoses
aldohexoses
R = H or CH2OH
EX. D-(+)-Glucose % an aldohexose which forms a six-membered ring hemiacetal

EX. D-(-)-Fructose % an ketohexose which forms a five-membered ring hemiacetal

Drawing Haworth Projection Formulas –

Six-Membered Ring Hemiacetals –

- draw a flat cyclohexane with hemiacetal ring oxygen in the upper right corner
5 O
- the hemiacetal carbon is on the right side of the ring @ C-1 4 1

3 2
- number the ring clockwise from C-1 to C-5
6
CH2OH
- C-6 is the -CH2OH group which points up in a D-sugar & down in an L-sugar 5 O
4 1

3 2

- the configurations @ C-2,C-3 & C-4 are determined from the following correlation:

Fischer Projection Haworth Projection

-OH Right -OH Down

-OH Left -OH Up

- the configuration @ C-1 is indeterminate (-OH can be either up or down)

EX. D-(+)- Galactose 1
CHO
6
OH
2
H OH
5
3 HO O OH
HO H H2 O H
4
4 OH H 1 +/or
HO H H H
3 2
5
H OH H OH
6
CH2OH

Fischer Projection Haworth Projection

Five-Membered Ring Hemiacetals –

- draw a flat cyclopentane (pointing “back”) with hemiacetal ring oxygen in the center
O

- the hemiacetal carbon is on the right side of the ring:

@ C-1 in aldopentoses or @ C-2 in ketohexoses (C-1 is a -CH2OH)

- number the ring clockwise from C-1 to C-4 (aldopentoses) or C-2 to C-5 (ketohexoses)

- C-5 or C-6 is the -CH2OH group which points up in a D-sugar & down in an L-sugar
5 6
HOCH2 HOCH2
O O 2 1
4 1 5 CH2OH
3 2 4 3

aldopentoses 2-ketohexoses

- the configurations @ C-2 & C-3 (aldopentoses) or @ C-3 & C-4 (ketohexoses) are determined
from the following correlation:

Fischer Projection Haworth Projection

-OH Right -OH Down

-OH Left -OH Up

- the configuration @ C-1 (aldopentoses) or @ C-2 (ketohexoses) is indeterminate (-OH can be

either up or down)

EX. D-(-)- Ribose % an aldopentose

1
CHO
2 5 O
H OH OH
H2 O HO
3
4 H H 1 +/or
H OH H H
4 HO 3 2 OH
H OH
5
CH2OH
Fischer Projection Haworth Projection
EX. D-(-)- Fructose % a 2-ketohexose
1
CH2OH
2
C O
3 6 O 1
HO H
H2 O HO OH
H 4
OH
5 H HO 2
H OH
5 +/or
H OH HO 4 3 H
6
CH2OH

Fischer Projection Haworth Projection

Conformations of Six-Membered Ring Hemiacetals –

- the most stable cyclic hemiacetal form for aldohexoses is the chair conformer

Drawing Chair Conformers for Aldohexoses –

- arrange a chair with the hemiacetal carbon (C-1) pointing down on the right

- place the hemiacetal oxygen in the upper right position 6

HOCH2
4 5 O
- number the ring clockwise from C-1 to C-5
2 1
3

- C-6 is the -CH2OH group which points up in a D-sugar & down in an L-sugar

- the configurations @ C-2, C-3 & C-4 are determined from the following correlation:

Fischer Projection Haworth Projection Chair Conformer

-OH Right -OH Down -OH Down

-OH Left -OH Up -OH Up

- the configuration @ C-1 is indeterminate (-OH can be either up or down)

- the most stable aldohexose chair conformations will have the most equatorial -OH’s

EX. D-(+)- Glucose

1
CHO
6
OH
H 2
OH H
5 O OH
3 H OH 4 6
H O
HO H H2 O H 5
4
4 OH H 1 +/or HO
H OH HO H HO 1 OH
3 2 2
H 5
OH 3 H OH
H OH
6 H H +/or
CH2OH

Fischer Projection Haworth Projection Chair Conformer

Anomers –

- diastereomers resulting from the indeterminate configuration at the hemiacetal carbon (C-1 or
C-2) where the -OH can point either up or down

Anomeric Carbon –

- the original carbonyl carbon (C=O) which reacts & becomes the cyclic hemiacetal carbon

- this position is C-1 in aldopentoses & aldohexoses and C-2 in ketohexoses R O

C
O H
- it is the only carbon in the ring with two oxygens attached

- anomers are also a class of epimers (diastereomeric sugars with identical configurations at every
stereocenter except one)

- anomers are distinguished as follows:

Name Configuration @ Anomeric Carbon

"-Anomer (Alpha) -OH Down

$-Anomer (Beta) -OH Up

Mutarotation –

- because anomers are diastereomers, they have unique physical properties

- therefore, the specific rotation ["] values for anomers will be different

- placing either the "-anomer or the $-anomer in solution results in a “drift” of the specific rotation
value ["] to a mutual value between the values of the two anomers

- the phenomenon of mutarotation is the result of an equilibrium which exists between the "-
anomer & the $-anomer in solution:
"-anomer º “open-chain” carbonyl º $-anomer

- for aldohexoses, the mutarotation value is always closer to the value for the $-anomer

- this indicates that the equilibrium mixture contains more of the more stable $-anomer

- the $-anomer is more stable because the -OH on the anomeric carbon (C-1) is up & equatorial
4 4
5 O 5 O

2
1 OH 2
1 H
3 up & equatorial 3 down & axial
H (more stable) OH (less stable)
β-Anomer α-Anomer
EX. D-(+)- Mannose
1
6
OH CHO 6
OH
2
5
O HO H 5
O
H H H 2O H OH
H H 2O 3 H
4 OH HO 1 HO H 4 OH HO 1

HO OH H 4
OH HO H
3 2 3 2
H H H 5
OH H H
6
CH2OH
α-D-Mannose β-D-Mannose
"Open-chain"
[α] = +150o [α] = +23o
(less than 1%)

- after equilibrium has been established, the mutarotation value for D-(+)-mannose is:

["]eq = +60o (closer to the specific rotation value for the $-anomer)

Naming Cyclic Monosaccharides –

- sugars are classified and named according to hemiacetal ring size:

Pyranoses –

- six-membered ring hemiacetals (from pyran, a six-membered oxygen heterocycle)

O
- pyranoses are the cyclic derivations of aldohexoses: Pyran
OH
CHO O
H2O
(CHOH)4 HO OH
CH2OH
HO OH
aldohexose pyranose

Furanoses –

- five-membered ring hemiacetals (from furan, a five-membered oxygen heterocycle)

- furanoses are the cyclic derivations of aldopentoses & ketohexoses: O

Furan
CH2OH
CHO HO
O R
C O
(CHOH)3 or H2O
(CHOH)3 OH R = H or CH2OH
CH2OH
CH2OH HO OH
aldopentose ketohexose furanose

- the complete name of a specific monosaccharide in its cyclic hemiacetal form would include the
prefix of that sugar’s name:

<" or $> - <D or L> - <sugar name prefix> - <pyran or furan> - ose
 EX ‘s
6
OH H
6
OH
HO
5
O H
6 O OH
5 O H 4
5
H O
H HO OH HO 4 H HO
4 OH H 1
5 H HO 2 H 1
H 1 H OH HO 2
1 OH
H OH 3 H OH
3 2 HO 4 3 H HO 3 2 OH
H OH H H
α-D-galactopyranose β-D-fructofuranose α-D-ribofuranose β-D-glucopyranose

- students are responsible for knowing the structural formulas of the following monosaccharides:

D-(+)-Glyceraldehyde (an aldotriose)

D-(-)-Ribose (an aldopentose)

D-(+)-Glucose (an aldohexose)

D-(+)-Galactose (an aldohexose)

D-(+)-Mannose (an aldohexose)

D-(-)-Fructose (an ketohexose)

- only the Fischer projection formulas require memorization – the Haworth projection & chair
conformer structural formulas are derived from the Fischer projection’s pattern of -OH’s

- note that there is no correlation between D/L (a drawing convention) & +/- (a physical property)

- students are only responsible for D & L structure (+ & - may be ignored)

REACTIONS OF MONOSACCHARIDES –

- because they are multifunctional compounds, monosaccharides exhibit the chemical behavior of
three unique functional groups – carbonyls, alcohols & hemiacetals

- the small amount of “open-chain” carbonyl form present in the equilibrium accounts for the
aldehyde/ketone reactions of monosaccharides

A. Epimerization –

- a base-catalyzed process where the acidic alpha-hydrogen ("-H) is removed & replaced, causing
the configuration at the alpha-carbon ("-C) to be racemized (creates epimers)

C O B C O
α α
H C OH HO C H B = OH , NH3, RNH2, R2NH, R3N,....

aldose or ketose aldose or ketose

Mechanism –

1 1
EX. CHO CHO
2 2
H OH HO H
OH
3 3
H OH H OH
4 4
H OH H OH
5 5
CH2OH CH2OH

D-ribose D-arabinose

B. Enediol Rearrangement –

- a base-catalyzed process where the carbonyl group migrates along the carbon chain

- note that aldoses & ketoses can thus interconvert under basic conditions

C O B CHOH
CHOH C O B = OH , NH3, RNH2, R2NH, R3N,....

aldose or ketose ketose or aldose

Mechanism –
 1
EX. CHO
1
CH2OH
2 2
H OH C O
OH
3 3
H OH H OH
4 4
H OH H OH
5 5
CH2OH CH2OH

D-ribose D-ribulose

- under basic conditions, monosaccharides will undergo both epimerization & enediol
rearrangement, resulting in complex product mixtures

- therefore, contact with alkaline reagents is mostly avoided

C. Reduction –

- the small amount of “open-chain” carbonyl form present in the equilibrium allows for conversion
of the carbonyl to an alcohol
CH2OH
CHO CH2OH
C O
(CHOH)n or RA (CHOH)n
(CHOH)n RA = NaBH4, H2/Ni, ........
CH2OH CH2OH
CH2OH
aldose ketose alditol

EX. 1 1
CHO CH2OH
2
H OH H 2
OH
3
HO H NaBH4 HO 3
H
4
HO H HO 4
H
5
H OH H 5
OH
6 6
CH2OH CH2OH

D-galactose D-galactitol (Dulcitol)

D. Oxidation –

- different oxidizing agents produce different sugar derivatives:

1) Bromine Water, Br2/H2O

- only the aldehyde group of an aldose reacts:

CHO COOH
Br2
(CHOH)n (CHOH)n
H2O
CH2OH CH2OH

aldose aldonic acid

 - ketoses do not react:
CH2OH
C O Br2
NR
(CHOH)n H2O
CH2OH
ketose

EX. 1 1
CHO COOH
2
H OH H 2
OH
3
HO H Br2 HO 3
H
4
H OH H2O H 4
OH
5
H OH H 5
OH
6 6
CH2OH CH2OH

D-glucose D-gluconic acid

2) Nitric Acid, HNO3

- both the aldehyde & primary alcohol groups of an aldose are oxidized:
CHO COOH
HNO3
(CHOH)n (CHOH)n
CH2OH COOH

aldose aldaric acid

- ketoses also react, giving more complex product mixtures:

CH2OH
COOH
C O HNO3
(CHOH)n-1 + other products
(CHOH)n
COOH
CH2OH
ketose aldaric acid

EX. 1 1
CHO COOH
2
HO H HO 2
H
HO 3
H HNO3 HO 3
H
4
H OH H 4
OH
5
H OH H 5
OH
6 6
CH2OH COOH

D-mannose D-mannaric acid

 3) Tollen’s Reagent, Ag(NH3)2+

- Tollen’s reagent provides a simple visible chemical test for aldehydes (a silver mirror is produced
upon oxidation indicating a “positive test”)

- other oxidizing agents, such as Fehling’s & Benedict’s solutions (copper(II) complexes) produce
similar observable results with aldehydes (a red precipitate indicates a positive test)

- all of these reagents are strongly basic, and therefore cause epimerization & enediol
rearrangement to occur with monosaccharides, resulting in complex product mixtures

- since enediol rearrangement converts ketoses to aldoses, ketoses are also ultimately oxidized
& give positive tests, making them indistinguishable from aldoses:
CH2OH
CHO COOH
C O
Ag(NH3)2
(CHOH)n or (CHOH)n + other products
(CHOH)n
CH2OH CH2OH
CH2OH
aldose ketose aldonic acid

- while Tollen’s reagent may not be useful for distinguishing aldoses from ketoses, it is useful for
identifying a certain class of carbohydrates:

Reducing Sugars, RS –

- sugars which reduce Tollen’s reagent (& related OA’s), becoming oxidized themselves

- include all aldoses & ketoses (which equilibrate in the cyclic hemiacetal form)

- exist as anomers & exhibit mutarotation α-anomer β-anomer

E. Ester Formation –

- all hydroxy groups in the monosaccharide react (like alcohols) with acid derivatives to produce
ester groups

Py
R(OH)n + Ac2O R(OAc)n + AcOH

R(OH)n = sugar, all OH's react, including hemiacetal OH

O
Ac = C CH3 (acetyl group); other acyl groups possible
O O
Ac2O = CH3 C O C CH3 (acetic anhydride); other acid derivatives possible

Py = (pyridine); other bases possible

N
EX.
6
OH 6
OAc
5
H O OH H
5
O OAc
H Ac2O H
4 OH H 1 4 OAc H 1
HO H Py AcO H
3 2 3 2
H OH H OAc

E. Ether Formation –

- all hydroxy groups in the monosaccharide react (like alcohols) with alkyl halides to produce ether
groups

Ag2O
R(OH)n + CH3I R(OCH3)n + AgI

R(OH)n = sugar, all OH's react, including hemiacetal OH

CH3 (Methyl) most common alkyl group; others possible

I (Iodo) most common leaving group; others possible

Ag2O (Silver oxide) most common base; others possible

EX.
6
OH 6
OCH3
5
H O OH H
5
O OCH3
H CH3I H
4 OH H 1 4 OCH3 H 1
HO H Ag2O CH3O H
3 2 3 2
H OH H OCH3

F. Osazone Formation –

- recall the reaction of carbonyls with hydrazines to produce hydrazones:

H
C O + H2N NH C N NH + H2O

- the first two carbons of both aldoses & ketoses react with phenylhydrazine to form a bis-
hydrazone known as an osazone

- hydrazone formation at the first carbonyl group is followed by oxidation of the "-carbon’s hydroxyl
group to a second carbonyl group which then forms the second hydrazone:
 CH O
CH OH
(CHOH)n
CH2OH
aldose CH N NH Ph NH2
H
or + 3 NH NH2 C N NH Ph + + NH3
CH2 OH (CHOH)n
phenylhydrazine
C O CH2OH
(CHOH)n osazone
CH2OH Ph =
ketose

- any difference at C-1 or C-2 is lost in the formation of osazones

- thus, C-2 epimers will form the same osazones (as will related aldoses & ketoses)

EX. 1
CHO 1
1
CHO
CH N NH Ph
2
H OH 2 HO 2
H
C N NH Ph
3
HO H 3 Ph NH NH2 3 3 Ph NH NH2 HO 3
H
HO H
4
H OH 4 H 4
OH
H H OH H
5
H OH 5 H 5
OH
H OH
6 6
CH2OH 6 CH2OH
CH2OH
D-glucose same osazone D-mannose

3 Ph NH NH2 H

1
CH2OH
2
C O
3
HO H
4
H OH
5
H OH Ph =
6
CH2OH

D-fructose

G. Glycoside Formation –

- recall that Tollen’s reagent (& related OA’s) identify reducing sugars

- this distinguishes them from nonreducing sugars which do not give positive Tollen’s tests

- this distinction is the result of the different functional groups present in these two cyclic
monosaccharide classes:

- the reducing sugar has a hemiacetal group which opens in water

- the nonreducing sugar has an acetal group which does not open in water:
 OH O O
C H 2O C C
OA OH
(C)n (C)n (C)n OA = Ag(NH3)2 ,.......
H H
O O O
cyclic hemiacetal open-chain carbonyl oxidizes
(aldose or ketose) (gives + test)

therefore; reducing sugars are hemiacetals

OR
C
H 2O OA
(C)n NR NR OA = Ag(NH3)2 ,.......
O
cyclic acetal won't open in H2O does not oxidize
(glycoside) (requires H ) (does not give + test)

therefore; nonreducing sugars are acetals (glycosides)

O
- Glycosides are cyclic acetal forms of sugars OR

- they are prepared by the acid-catalyzed reaction of an alcohol with a pyranose or furanose

- note that only the anomeric (hemiacetal) carbon’s hydroxyl group reacts under these conditions

OH OH
O O
H
HO OH + ROH HO OR + H2 O

HO OH HO OH

pyranose pyranoside

HO HO
O R' O R'
H
OH + ROH OR + H2 O

HO OH HO OH

furanose furanoside R' = H or CH2OH

ROH = CH3OH, CH3CH2OH, PhOH, another monosaccharide,.........

Naming Glycosides –

- place R group (alkyl or aryl) name in front (separate word)

- change ending from e Y ide

 EX ‘s Preparation & naming of glycosides
H H
6
OH 6
OH
4
5
H O 4 H O
5
HO H HO
+ CH3CH2 OH + H2 O
HO 2
1 OH HO 2
1 OCH2CH3
3 H OH 3 H OH
H H H H
β-D-glucopyranose ethyl β-D-glucopyranoside

6 1 6 1
O O
HO OH HO OH
5 H HO 2 H 5 H HO 2
+ H2 O
H OH + CH3 OH H OCH3
HO 4 3 H HO 4 3 H

α-D-fructofuranose methyl α-D-fructofuranoside

- note the distinct contrast in chemical behavior between reducing & nonreducing sugars:

Nonreducing Sugars, NRS –

- sugars which do not reduce Tollen’s reagent (& related OA’s)

- are glycosides (cyclic acetals)

- do not equilibrate in water with the “open-chain” carbonyl form

- do not exhibit anomerism or mutarotation α-anomer β-anomer

II. DISACCHARIDES –
- sugars composed of two monosaccharides connected in glycoside (acetal) linkages

- the glycosidic bond is formed between the anomeric carbon of the “first” monosaccharide unit &
the hydroxyl group of the “second” monosaccharide unit

- disaccharides can be categorized according to the position of the hydroxyl group on the “second”
monosaccharide unit making up the glycoside:

OH Position on 2nd MS Unit Disaccharide Class

@ C-4 1÷4' Glycoside

@ C-6 1÷6' Glycoside

@ C-1 1÷1' Glycoside

@ C-2 1÷2' Glycoside

- disaccharides can be categorized according to the configuration at the anomeric carbon of the first
monosaccharide unit:

“OR” Position on Anomeric C of 1st MS Unit Disaccharide Class

Up $-Glycoside (beta)

Down α-Glycoside (alpha)

- typical monosaccharide units found in naturally occurring disaccharides are glucose, galactose &
fructose

÷4' Glycosides –
A. 1÷

- these represent the most common naturally occurring disaccharides

- the anomeric carbon (C-1) of the first MS unit is connected through the C-4 OH of the second
MS unit

1) Maltose –

- this disaccharide is a hydrolysis product of starch:

H H
Starch Maltose 2 Glucose
H2O, ∆ H2O, ∆

- maltose can be described as: two glucose units in an α(1÷

÷4') glycoside (glucoside)

NRS Unit

H
6
OH
4
5
H O
HO
HO 1 H
2 RS Unit
3 H OH H
H 6' OH
4' H O
O 5'
α(1 4') glycoside 3'
2'
HO 1' OH
H OH
Maltose H H
+/or β shown; α possible
4-O-(α-D-glucopyranosyl)-β-D-glucopyranose
2) Cellobiose –

- this disaccharide is a hydrolysis product of cellulose:

H H
Cellulose Cellobiose 2 Glucose
H2O, ∆ H2O, ∆

- cellobiose can be described as: two glucose units in a β (1÷

÷4') glycoside (glucoside)

NRS Unit RS Unit

H
OH
4 6
H O H
5 6' OH
HO 4' H O
HO 1 O 5'
2 2'
3 H OH HO 3' 1' H
H H H OH
β(1 4') glycoside H OH +/or α shown; β possible

Cellobiose
4-O-(β-D-glucopyranosyl)-α-D-glucopyranose

3) Lactose –

- a naturally occurring disaccharide found in the milk of mammals such as cows & humans

- lactose yields galactose & glucose upon hydrolysis:

H
Lactose Galactose + Glucose
H2O, ∆

- lactose can be described as: galactose (nonreducing) & glucose (reducing) units in a
β (1÷
÷4') glycoside (galactoside)

NRS Unit RS Unit

(galactose) (glucose)

OH
OH
4 6
H O H
5 6' OH
H 4' H O
HO 1 O 5'
2 2'
3 H OH HO 3' 1' OH
H H H OH
H H
β(1 4') glycoside +/or β shown; α possible
Lactose
4-O-(β-D-galactopyranosyl)-β-D-glucopyranose
 ÷6' Glycosides –
B. 1÷

- the anomeric carbon (C-1) of the first MS unit is connected through the C-6 OH of the second
MS unit

Gentiobiose –

- this disaccharide is incorporated into crocin, the principle component of saffron

H
Gentiobiose 2 Glucose
H2O, ∆

- gentiobiose can be described as: two glucose units in a β (1÷

÷6') glycoside (glucoside)

NRS Unit

H
OH
4 6
H O β(1 6') glycoside
5
HO
HO 2
1 O
3 H OH
H HH 6'
RS Unit
4' H O
HO 5'
2'
HO 3' 1' H
H OH
H OH +/or α shown; β possible

Gentiobiose
6-O-(β-D-glucopyranosyl)-α-D-glucopyranose

÷2' Glycosides –
C. 1÷

- these compounds & their related 1÷1' glycosides represent the nonreducing disaccharides

- the glycosidic linkage involves the anomeric carbons from both monosaccharide units

Sucrose –

- a naturally occurring disaccharide found in sugar cane & sugar beets (table sugar)

- hydrolysis of sucrose yields glucose & fructose

H
Sucrose Glucose + Fructose
H2O, ∆

- sucrose can be described two ways:

glucose & fructose units in an α(1÷

÷2') glycoside (glucoside)

or; fructose & glucose units in a β (2'÷

÷1) glycoside (fructoside)
 H
6
OH
4
5
H O
NRS Unit (glucose) HO
HO 1 H
2
3 H OH α(1 2') glucoside
H
O
6'
O β(2' 1) fructoside
HO 5' 2'
NRS Unit (fructose) H HO OH
H 1'
HO 4' 3' H

Sucrose
α-D-glucopyranosyl-β-D-fructofuranoside
or
β-D-fructofuranosyl-α-D-glucopyranoside

Naming Disaccharides –

- the following systematic nomenclature method is used for disaccharides:

1) identify the hydroxyl oxygen making the glycosidic bond as a number prefix followed by O

EX. 4-O- prefix indicates the RS unit’s C-4 OH makes the glycoside

2) name the NRS unit (left), changing the ending from ose ÷ osyl

3) name the RS unit (right) as a normal cyclic monosaccharide & indicate the anomer present

- students are not responsible for common names of disaccharides

EX. OH
OH
4 6
H O H
5 6' OH
H 4' H O
HO 1 O 5'
2 2'
3 H OH HO 3' 1' H
H H H OH
H OH
Lactose
4-O-(β-D-galactopyranosyl)-α-D-glucopyranose

III. POLYSACCHARIDES –
- macromolecules made up of long chains of monosaccharide units joined in glycosidic linkages

- the most common polysaccharides are polymers of glucose

A. Starch –

- the glucose (energy) storage form for plants

- starch contains two components, which are separable on the basis of water solubility

soluble H H
Amylose Maltose Glucose
H 2O H 2O
H2 O 20%
Starch
insoluble H H
Amylopectin Maltose + Isomaltose Glucose
H2O H 2O
80%

1) Amylose –

- a linear polymer of glucose units in α(1÷4') glycosides (glucosides)

H OH
H
O
O H H OH
HO H
H
H OH
O
( O
HO H H OH
H OH H
O
α(1 4') glycoside H O )n
HO HH OH
H OH H
Amylose H O O
HO H
(n ~ 103 's)
H OH
H O

2) Amylopectin –

- a branched polymer of glucose units in α(1÷4') glycosides with α(1÷6') glycoside branches

H OH
H
O O
HO HH OH
H OH H
H O O
H OH
H HO H
O OH α(1 6') glycoside branch
O H H OH H
HO H
H O
H
H OH
O
( O
HO H H
H OH H
O
α(1 4') glycoside H O )n
HO HH OH
H OH H
Amylopectin H O O
HO H
(n ~ 104 total) H OH
H O
(n ~ 20 -25 between branches)
B. Glycogen –

- the glucose (energy) storage form for animals

- a branched polymer of glucose units in α(1÷4') glycosides with α(1÷6') glycoside branches

- so; same as amylopectin, but more highly branched

H OH
H
O O
HO HH OH
H OH H
H O O
H OH
H HO H
O OH α(1 6') glycoside branch
O H H OH H
HO H
H O
H
H OH
O
( O
HO H H
H OH H
O
α(1 4') glycoside H O )n
HO HH OH
H OH H
Glycogen H O O
HO H
(n ~ 106 total) H OH
H O
(n ~ 10 -12 between branches)

- the increased branching in glycogen provides more available glucose “ends” to satisfy the greater
metabolic demand of motile organisms

C. Cellulose –

- the principal component of plant cell walls, providing the plant’s structural strength & rigidity

- a linear polymer of glucose units in β(1÷4') glycosides (glucosides)

β(1 4') glycoside

H OH
H OH
H H OH
O H
O H H OH
O O( O
HO O )n H
HO O O
H OH HO
H H H OH O
H H H OH HO
H H OH
H
H H
Cellulose
(n ~ 103 's)

- most organisms cannot digest cellulose because they lack the enzyme which catalyzes the
hydrolysis of the β−glucoside